CN118638010A - Method for preparing perfluorinated acid ester from chlorofluoro-acid ester - Google Patents

Method for preparing perfluorinated acid ester from chlorofluoro-acid ester Download PDF

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CN118638010A
CN118638010A CN202411104141.8A CN202411104141A CN118638010A CN 118638010 A CN118638010 A CN 118638010A CN 202411104141 A CN202411104141 A CN 202411104141A CN 118638010 A CN118638010 A CN 118638010A
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宋昌平
史翔
王丽
孙振钰
李景通
郑魁星
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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Abstract

The invention relates to the technical field of fluoride engineering, in particular to a method for preparing perfluorinated acid ester by using fluoroformate, wherein the perfluorinated acid ester is prepared by reacting fluoroformate and perfluorinated olefin in an equimolar ratio in a micro-channel reactor, wherein hydrofluoroether is used as a solvent, and bromine-based organic salt or iodine-based organic salt is used as a catalyst; according to the method for preparing the perfluorinated acid ester, provided by the invention, the hydrofluoroether is used as a solvent, the bromo-based organic salt or the iodo-based organic salt is used as a catalyst, so that the whole system is in a liquid phase, no additional metal element is introduced, the bromine atom and the iodine atom are larger in size, the formed carbanion intermediate product is unstable, the leaving of bromide ions/iodide ions is facilitated, excessive reaction is avoided, and the generated byproducts such as hexafluoropropylene polymer and the like are obviously reduced.

Description

Method for preparing perfluorinated acid ester from chlorofluoro-acid ester
Technical Field
The invention relates to the technical field of fluorine chemical industry, in particular to a method for preparing perfluoro acid ester from chlorofluoro acid ester.
Background
The fluoroformate substance is a methylation reagent synthesized by carbonyl fluoride and alcohol substances under the condition of excessive carbonyl fluoride, and can be used for synthesizing products such as hydrofluoroether perfluoro isopropyl methyl ether (HFE-i 7100), perfluoro isobutyl methyl ether and the like.
However, the fluoroformate can also undergo addition reaction to synthesize longer-chain perfluoroalkyl carboxylate substances due to the presence of acyl fluoride functional groups, and can also be used for synthesizing low-GWP electrical insulation gas perfluoroisobutyronitrile. The method for obtaining the long-chain ester by adopting the fluoroformate addition method has the advantages of more flexible raw material selection, higher reaction activity, fewer byproducts and higher atom utilization rate. However, the research on the reaction is limited to theory and pilot synthesis, and the industrialization of the reaction still has a great difficulty.
In the prior art, the article (Journal of Fluorine Chemistry, 56 (1992) 93-99) mentions that the chlorofluoro-formate can react with hexafluoropropylene to synthesize perfluoroisobutyric acid ester substances by a mechanism, but no industrialized synthesis process or method is proposed, and the adopted catalyst is also conventional sodium fluoride, and the reaction is heterogeneous solid-liquid reaction. Under the system, the reaction time is as long as 6 hours, and industrialization cannot be realized. Under the conditions, the catalysis of fluoride salt can lead to self-polymerization of hexafluoropropylene, so that hexafluoropropylene polymers are generated, the boiling point of the hexafluoropropylene polymers is close to that of related esters, and the hexafluoropropylene polymers are difficult to separate.
Chinese patent document CN 108395382A (application No. 201810233636.9) discloses a method for synthesizing sevoflurane isobutyrate by one-pot reaction of chloroformate and hexafluoropropylene in the presence of aprotic solvent and fluoride salt, which also selects fluoride salt as catalyst, and is very easy to produce hexafluoropropylene self-polymer. The greater problem is that the chloroformate is used as a starting material, and the inability of the chlorine element in the material to form heptafluoroisobutyrate results in the formation of a byproduct chloride salt, which is consumed in a significant amount from the catalyst to the starting material.
Thus, although some technologies have mentioned the mechanism of synthesizing perfluorinated acid esters by an addition method, fluoride salts are generally selected as catalysts, wherein the solubility of inorganic fluoride salts in organic solvents is extremely low; while organofluoro salts are too active, resulting in more by-product. Meanwhile, the reaction device generally selects a reaction kettle, the reaction mode carried out in the reaction kettle is liquid film reaction, and the reaction liquid film of the reaction kettle is small in specific surface area and low in reaction efficiency, so that the industrial production is not facilitated. If a non-fluoroformate material is used, atoms are not fully utilized, and fluoride salts are consumed from the catalyst to the material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for preparing perfluoroacid ester by using chlorofluoroacid ester, which uses bromine/iodine-based organic salt as a catalyst and hydrofluoroether as a solvent to enable the reaction to react in a micro-channel reactor under a full liquid phase condition, so that the selectivity and the conversion rate are effectively improved, and the reaction time and the hazardous waste output are effectively controlled.
In order to achieve the technical effects, the invention adopts the following technical scheme:
A method for preparing perfluorinated acid ester by using chlorofluoro ester takes the chlorofluoro ester and perfluorinated olefin with equal molar ratio as reaction raw materials, hydrofluoroether as solvent, and bromo-or iodo-organic salt as catalyst, and then the perfluorinated acid ester is obtained by reaction in a micro-channel reactor;
the method specifically comprises the following steps:
s1, putting a catalyst into a solvent, and preheating to obtain a mixed solution for standby;
s2, injecting the reaction raw materials and the mixed solution into a micro-channel reactor together, reacting, rectifying and separating to obtain the perfluorinated acid ester.
According to the method for preparing the perfluorinated acid ester, provided by the invention, the hydrofluoroether is used as a solvent, the bromo-based organic salt or the iodo-based organic salt is used as a catalyst, so that the whole system is in a liquid phase, no additional metal element is introduced, the bromine atom and the iodine atom are larger in size, the formed carbanion intermediate product is unstable, the leaving of bromide ions/iodide ions is facilitated, excessive reaction is avoided, and the generated byproducts such as hexafluoropropylene polymer and the like are obviously reduced.
Meanwhile, by matching the bromo-or iodo-organic salt with the hydrofluoroether, the hydrofluoroether has a fluorine-philic chain and an ester-philic chain, so that the catalyst and the reaction raw materials are dissolved in a solvent, and a homogeneous system is formed at the reaction temperature, thereby facilitating the reaction in the microchannel reactor to prepare the product. The product produced by the micro-channel reactor is in a liquid phase state, and after the product is separated by rectification, the solvent hydrofluoroether, the catalyst and the byproducts can be separated at the same time, so that the solvent can be regenerated and reused.
Preferably, in step S1, the mass ratio of the catalyst to the solvent is (5-50): 100; it is further preferred that the mass ratio of the catalyst to the solvent is (5-15): 100.
Preferably, in the step S2, the feeding mass ratio of the reaction raw materials to the mixed solution is 1 (10-50); further preferably, the ratio of the reaction raw materials to the mixed solution is 1 (20-30).
Preferably, in step S2, the reaction temperature is from 30℃to 100 ℃.
Preferably, the chloroformate is selected from methyl chloroformate or ethyl chloroformate, and the perfluoroolefin is selected from hexafluoropropylene or octafluoro-1-butene; further preferably, octafluoro-1-butene is used as the perfluoroolefin.
Preferably, the catalyst is selected from at least one of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium iodide, n-butyltriphenylphosphine bromide, n-butyltriphenylphosphine iodide, tetrabutylphosphine bromide or tetrabutylphosphine iodide; further preferably, the catalyst is selected from at least one of n-butyltriphenylphosphine bromide, n-butyltriphenylphosphine iodide, tetrabutylphosphine bromide or tetrabutylphosphine iodide.
When the catalyst is organic phosphine salt, the boiling point of the material is higher, the stability at high temperature is better, and the solubility in the hydrofluoroether is higher.
Preferably, the hydrofluoroether is selected from
CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3、
CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3、
CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3、
CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3、
CF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3 Or (b)
CF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3 At least one of them.
The hydrofluoroethers have long main carbon chains and boiling points above 150 ℃, and can be stably kept in a liquid phase under high-temperature reaction conditions. In contrast, conventional low boiling hydrofluoroethers such as HFE-7100 and HFE-7300 are vaporized at about 50℃and cannot maintain the liquid phase of the whole system during the reaction.
By using the hydrofluoroether as a solvent, the reaction system is homogeneous at any time, and the dissolution performance of the hydrofluoroether can be matched with a certain pressure, so that the hydrofluoroether does not generate obvious gasification in the reaction process, and the formation of plug flow in the microchannel reactor is avoided. Because no solid material is formed, the whole micro-channel reactor is liquid phase, compared with the fixed bed catalytic gas phase reaction, the micro-channel reactor has the advantages of better heat transfer performance, lower reaction temperature, convenient replacement of catalyst and solvent, no coking phenomenon and the like, and is more suitable for industrial production.
Preferably, the microchannel reactor comprises a premixer and a reaction channel, the premixer being used to mix the injected fluids.
The beneficial effects of the invention are as follows:
According to the method provided by the invention, the bromine-based organic salt or the iodine-based organic salt is selected as the catalyst and the hydrofluoroether is selected as the solvent, so that the existence or generation of solids in the whole system is ensured, the operation and maintenance requirements of the microchannel reactor in the use process are reduced, and the solvent can be regenerated through rectification after the reaction runs for a long time. And the metal element is not contained in the material, and the reaction residual liquid can be completely converted through simple treatment, so that the subsequent treatment burden is reduced, and the production amount of solid dangerous waste is reduced.
Detailed Description
The present invention will be further illustrated with reference to examples and comparative examples.
The raw materials and devices used in each example and comparative example are all commonly used and commercially available materials and devices in the art, for example, a microchannel reactor with a premixer provided in chinese patent document CN 114130326A (application No. 202111516043.1) may be selected as the microchannel reactor, and a person skilled in the art may select other microchannel reactors with premixers according to actual needs in specific applications. The specific sources of other raw materials are not described in detail herein.
Example 1
The method for preparing the perfluoroisobutyric acid methyl ester from the chlorofluoro methyl ester comprises the following specific steps:
(1) Firstly mixing CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3 and CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3 in equal volume, then adding tetrapropylammonium bromide and tetrabutylammonium iodide with equal mass ratio to prepare a mixed solution of catalyst and solvent with mass ratio of 5:100, and heating the solution to 60 ℃ for standby;
(2) At the inlet of a micro-channel premixer with the equivalent diameter of a channel of 100 mu m and the total length of a main reaction zone of 30m, introducing mixed solution and methyl chlorofluoroate and hexafluoropropylene with equal molar ratio, wherein the total length of the premixer is 0.5m, the mass feeding ratio of raw materials to the mixed solution is 1:50, the flow speed of the mixed materials is 1m/min, and the reaction temperature is controlled to be 30 ℃;
(3) After rectification, the methyl perfluoroisobutyrate with the purity of 99.5 percent is obtained, the reaction selectivity is 89.7 percent, and the conversion rate is 82.1 percent. The product structure characterization data are as follows ：1H NMR (600 MHz,CDCl3)δ3.89(s,3H);19F NMR(600 MHz,CDCl3)δ-76.15～-76.17(d,J＝12 Hz,6H),-183.02～-183.11(m,J＝54Hz,1H).
Example 2
The method for preparing the perfluoroisobutyric acid ethyl ester by using the ethyl chloroformate comprises the following specific steps:
(1) Adding n-butyl triphenylphosphine bromide and n-butyl triphenylphosphine iodide into CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3 in equal mass ratio to prepare a mixed solution of catalyst and solvent in a mass ratio of 50:100, and heating the solution to 100 ℃ for standby;
(2) At the inlet of a micro-channel premixer with the equivalent diameter of a channel of 100 mu m and the total length of a main reaction zone of 25m, introducing a mixed solution and ethyl chlorofluoroate and hexafluoropropylene with equal molar ratio, wherein the total length of the premixer is 0.5m, the mass feeding ratio of raw materials to the mixed solution is 1:30, the flow speed of the mixed materials is 1m/min, and the reaction temperature is controlled to be 100 ℃;
(3) After rectification, ethyl perfluoroisobutyrate with the purity of 99.3 percent is obtained, the reaction selectivity is 91.5 percent, and the conversion rate is 90.9 percent. The product structure characterization data are as follows ：1H NMR(600 MHz,CDCl3)δ4.53～4.48(m,2H),1.42～1.38(t,3H);19F NMR(600 MHz,CDCl3)δ -76.44～-76.46(d,J＝12Hz,6F),-183.17～-183.26(m,1F).
Example 3
The method for preparing the perfluoro-ethyl isovalerate by using the ethyl chloroformate comprises the following specific steps:
(1) Adding catalyst tetrabutyl phosphine bromide into CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2O -CH2CH3 to prepare mixed solution with the mass ratio of the catalyst to the solvent being 15:100, and preheating the liquid to 80 ℃ for standby;
(2) At the inlet of a micro-channel premixer with the equivalent diameter of a channel of 100 mu m and the total length of a main reaction zone of 25m, introducing a mixed solution, ethyl chlorofluoroformate and octafluoro-1-butene in an equimolar ratio, wherein the total length of the premixer is 0.5m, the mass feeding ratio of raw materials to the mixed solution is 1:20, the flow speed of the mixed materials is 1m/min, and the reaction temperature is controlled to be 70 ℃;
(3) After rectification, ethyl perfluoro isovalerate with the purity of 99.4 percent is obtained, the reaction selectivity is 91.0 percent, and the conversion rate is 88.8 percent. Product structure characterization data as follows ：1H NMR(600 MHz,CDCl3)δ3.79~3.74（m,2H）,1.28～1.26（t,3H）;19F NMR(600 MHz,CDCl3)δ -70.78～-70.81(m,3F),-80.79～-80.81(m,3F),-86.26～-86.29(m,2F),-118.78～-118.81(m,2F),-182.39～-182.48(m,1F). after 10 days of continuous operation, both the reaction selectivity and conversion of the product maintained the initial levels.
Example 4
The method for preparing the perfluoro-methyl isovalerate from the methyl chloroformate comprises the following specific steps:
(1) Mixing CF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3 and CF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3 in equal volume, adding tetrabutyl phosphine iodide serving as a catalyst into the mixture to prepare a mixed solution with the mass ratio of the catalyst to the solvent of 50:100, and preheating the liquid to 50 ℃ for later use;
(2) At the inlet of a micro-channel premixer with the equivalent diameter of a channel of 100 mu m and the total length of a main reaction zone of 30m, introducing mixed solution, methyl chlorofluoroate and octafluoro-1-butene in an equimolar ratio, wherein the total length of the premixer is 0.5m, the mass feeding ratio of raw materials to the mixed solution is 1:10, the flow speed of the mixed materials is 1m/min, and the reaction temperature is controlled to be 50 ℃;
(3) After rectification, the perfluoro-methyl isovalerate with the purity of 99.4 percent is obtained, the reaction selectivity is 90.2 percent, and the conversion rate is 85.0 percent. The product structure characterization data are as follows ：1H NMR(600 MHz,CDCl3)δ3.41(s,3H);19F NMR(600 MHz,CDCl3)δ -70.79～-70.81(m,3F),-80.78～-80.80(m,3F),-86.26～-86.29(m,2F),-118.77～-118.80(m,2F),-182.39～-182.48(m,1F).
Comparative example 1
The method for preparing the perfluoroisobutyric acid methyl ester from the chlorofluoro methyl ester comprises the following specific steps:
taking a 100L reaction kettle as reaction equipment, adding 200g of 2-perfluorobutane benzothiazole as a catalyst, then adding 70L of diethylene glycol dimethyl ether solution, finally adding 312g of methyl chloroformate and 600g of hexafluoropropylene, heating the reaction kettle at 100 ℃ to the highest pressure of 1MPa, reacting for 3 hours, rectifying to obtain the methyl perfluoroisobutyrate with the purity of 99.1%, the reaction selectivity of 87.5% and the conversion rate of 78.0%. The reaction selectivity, conversion and reaction time are all significantly less than those of the examples. It should be noted that this system requires a high temperature reaction, and does not react at 30℃to obtain the desired product.
Comparative example 2
The method for preparing the perfluoroisobutyric acid ethyl ester from the ethyl chloroformate comprises the following specific steps of:
Taking a 50L reaction kettle as reaction equipment, adding 200g of cesium fluoride as a catalyst, then adding 156g of ethyl chlorofluoroate and 300g of hexafluoropropylene, adding into 25L of ethylene glycol dimethyl ether solution, heating at 150 ℃, reacting for 6 hours, and rectifying to obtain a ethyl perfluoroisobutyrate product with the purity of 99.2%, wherein the selectivity is 88.7%, and the conversion rate is 77.5%. The reaction selectivity, conversion, productivity and reaction time are all significantly less than those of the examples. The main impurity produced is hexafluoropropylene dimer, ethyl chloroformate cannot react sufficiently due to excessive loss of hexafluoropropylene, and the conversion rate is lowered.
Comparative example 3
The method for preparing the perfluoro-ethyl isovalerate by using the ethyl fluoformate comprises the following specific steps of:
A tube with the length of 80cm and the diameter of 2.5cm is used as a fixed bed reactor, a tubular fixed bed reactor with the total volume of 30L is used as reaction equipment, the catalyst is formed by mixing aluminum fluoride and potassium fluoride with the same mass, all the tubes are filled, the heating temperature is up to 190 ℃, the equal molar ratio of ethyl chlorofluoroate to octafluoro-1-butene is put into the reactor together, the residence time is maintained for 3min, and when the reaction is started, the purity of the product of the ethyl perfluoroisovalerate is 99.3%, the selectivity reaches 90.2%, and the conversion rate is 70.1%. After 10 days of operation, the selectivity was reduced to 88.1% and the conversion was reduced to 65%. There is always a trend towards reduced selectivity and conversion with longer run times. After disassembling the reactor, it was found that coking conditions were difficult to clean up and replace, which was also a major factor in the decrease of catalytic activity.
Comparative example 4
The method for preparing perfluoro-methyl isovalerate from methyl chloroformate comprises the following specific steps:
200g of tetrabutyl phosphine iodide is added into 100L spray tower as reaction equipment, and is taken as a catalyst, 312g of methyl chloroformate and 800g of octafluoro-1-butene are added into 50L of mixed solution of tetraethyl glycol dimethyl ether 、0.5LCF3CF2CF2O -CF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3 and 0.5LCF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2O -CF(CF3)CF2OCH2CH3, heating is carried out at 90 ℃, the highest reaction pressure reaches 1MPa, the reaction is carried out for 4 hours, and the perfluoro-methyl isovalerate product with 99% purity is obtained after rectification, the selectivity is 87.7%, and the conversion rate is 80.1%. The conversion rate is obviously improved compared with other comparative examples by using the same catalyst and reaction system in comparative example 4, but the amplification effect is obvious compared with a micro-channel reactor under the same condition due to the larger gas phase space of a reaction kettle and larger equipment size, so that the catalyst and the reaction system have safety risks and are not suitable for industrial mass production.
Comparative example 5
The specific procedure of this comparative example differs from that of example 1 in that in step (1), the catalyst used equal amounts of tetrapropylammonium fluoride instead of tetrapropylammonium bromide and tetrabutylammonium iodide, with the other conditions being the same as in example 1.
After rectification, methyl perfluoroisobutyrate is obtained with 99.4% purity, the reaction selectivity is 82.1%, the conversion rate is 75.5%, and the conversion rate is greatly different from that of the example 1 because the organic fluoride salt is used as a catalyst, and more hexafluoropropylene two-addition byproducts are generated.
Comparative example 6
The specific procedure of this comparative example differs from that of example 1 in that in step (1), tetraethyleneglycol dimethyl ether was used in the same amount as in example 1 instead of CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3 and CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3,.
After rectification, the purity of the perfluoro-methyl isobutyrate is 99.1 percent, the reaction selectivity is 83.5 percent and the conversion rate is 70.1 percent. This is because the solvent does not use hydrofluoroether, and it is not ensured that the reaction system always remains in a full liquid phase state, which results in significant plug flow during the reaction process and a serious decrease in conversion rate.

Claims (10)

1. A method for preparing perfluorinated acid ester by using chlorofluoro ester is characterized in that the perfluorinated acid ester is prepared by reacting in a micro-channel reactor by taking chlorofluoro ester and perfluorinated olefin in an equimolar ratio as reaction raw materials, hydrofluoroether as a solvent and bromine-based organic salt or iodine-based organic salt as a catalyst;
the method specifically comprises the following steps:
s1, putting a catalyst into a solvent, and preheating to obtain a mixed solution for standby;
s2, injecting the reaction raw materials and the mixed solution into a micro-channel reactor together, reacting, rectifying and separating to obtain the perfluorinated acid ester.
2. The method for producing a perfluoroacid ester from a chloroformate according to claim 1, wherein the mass ratio of the catalyst to the solvent in step S1 is (5-50): 100.
3. The method for producing a perfluoroacid ester from a chloroformate according to claim 2, wherein the mass ratio of the catalyst to the solvent in the step S1 is (5-15): 100.
4. The method for producing a perfluoroacid ester from a chlorofluoro acid ester according to claim 1, wherein in step S2, the ratio by mass of the reaction raw material to the mixed solution is 1 (10-50).
5. The method for producing a perfluoroacid ester from a chlorofluoro acid ester according to claim 4, wherein in step S2, the ratio by mass of the reaction raw material to the mixed solution is 1 (20-30).
6. The method for preparing a perfluoroacid ester from a chloroformate according to claim 1, wherein the reaction temperature in step S2 is 30 ℃ to 100 ℃.
7. The process for preparing a perfluoroacid ester from a chloroformate according to claim 1, wherein the chloroformate is selected from methyl chloroformate or ethyl chloroformate and the perfluoroolefin is selected from hexafluoropropylene or octafluoro-1-butene.
8. The method for preparing a perfluoroacid ester from a chloroformate according to claim 1, wherein the catalyst is at least one selected from the group consisting of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium iodide, n-butyltriphenylphosphine bromide, n-butyltriphenylphosphine iodide, tetrabutylphosphine bromide and tetrabutylphosphine iodide.
9. The method for preparing a perfluoroacid ester from a chloroformate according to claim 1, wherein the hydrofluoroether is selected from the group consisting of
CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3、
CF3OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3、
CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3、
CF3CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3、
CF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH3 Or (b)
CF3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3)CF2OCH2CH3 At least one of them.
10. The method of preparing a perfluoroacid ester according to claim 1, wherein the microchannel reactor comprises a premixer and a reaction channel, the premixer being configured to mix the injected fluid.
CN202411104141.8A 2024-08-13 Method for preparing perfluorinated acid ester from chlorofluoro-acid ester Active CN118638010B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1174685A (en) * 1976-12-02 1984-09-18 Carl G. Krespan Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US4612143A (en) * 1984-09-17 1986-09-16 Societe Nationale Des Poudres Et Explosifs Process for the preparation of fluoroformates
US20110136713A1 (en) * 2008-08-11 2011-06-09 Solvay Solexis S.P.A. Hydrofluoroalcohols with improved thermal and chemical stability
CN108395382A (en) * 2018-03-14 2018-08-14 黎明化工研究设计院有限责任公司 Method for synthesizing perfluoroisobutyronitrile
US20190119192A1 (en) * 2016-03-31 2019-04-25 Solvay Specialty Polymers Italy S.P.A. Method for the manufacture of fluorinated compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1174685A (en) * 1976-12-02 1984-09-18 Carl G. Krespan Polyfluoroallyloxy compounds, their preparation and copolymers therefrom
US4612143A (en) * 1984-09-17 1986-09-16 Societe Nationale Des Poudres Et Explosifs Process for the preparation of fluoroformates
US20110136713A1 (en) * 2008-08-11 2011-06-09 Solvay Solexis S.P.A. Hydrofluoroalcohols with improved thermal and chemical stability
US20190119192A1 (en) * 2016-03-31 2019-04-25 Solvay Specialty Polymers Italy S.P.A. Method for the manufacture of fluorinated compounds
CN108395382A (en) * 2018-03-14 2018-08-14 黎明化工研究设计院有限责任公司 Method for synthesizing perfluoroisobutyronitrile

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